Solvent‐Dependent Oxidative Addition and Reductive Elimination of H2 Across a Gallium‐Zinc Bond. Issue 36 (4th August 2022)

• Record Type: Journal Article
• Authors: Morris, Louis J.; Rajeshkumar, Thayalan; Okumura, Akira; Maron, Laurent; Okuda, Jun
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 36(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-08-04
• Subjects: Dehydrogenation -- Heterometallic Complexes -- Hydrogenation -- Main Group Compounds -- Solvent Effects; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202208855
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: H2 adds reversibly across the metal‐metal bond of [(BDI)Ga(H)−Zn(tmeda)(thf)][BAr4 F ] (BDI=[HC{C(CH3 )N(2, 6‐ i Pr2 ‐C6 H3 )}2 ] −, TMEDA= N, N, N′, N′ ‐tetramethylethylenediamine, BAr4 F− =[B(C6 H3 ‐3, 5‐(CF3 )2 )4 ] − ). Due to the stabilising effect of solvent coordination, hydrogenation products [(BDI)GaH2 ] and [(tmeda)ZnH(thf)][BAr4 F ] are favoured in THF solution, but THF‐free mixtures of [(BDI)GaH2 ] and [(tmeda)ZnH(OEt2 )][BAr4 F ] are predisposed towards entropically driven dehydrogenation to [(BDI)Ga(H)−Zn(tmeda)][BAr4 F ] in fluorobenzene solution. Abstract : Dihydrogen reversibly adds across the Ga−Zn bond of a heterobimetallic cation. Oxidative addition is favoured in THF solution where the hydrogenation products are stabilized, but in fluorobenzene, reductive elimination of H2 is promoted by the Lewis‐acidic zinc hydride cation.